Патент USA US2119882код для вставки
Patented June 7, 1938 2,119,882 UNITED STATES PATENT OFFICE 2,119,882 ALIINOTRIFLUOROMETHYLeARYL- SUL PHONIC ACIDS AND PROCESS OF PRE PARING THEM Herbert Kracker and Fritz Herrlein, Frank fort-on-the-Main-Hochst, Germany, as signors to General Aniline Works, Inc., New York, N. Y., a corporation of Dela ware N0 Drawing. Application September 27, 1935, Serial No. 42,512. In Germany 00 tober 3, 1934 7 Claims. This invention relates to aminotrifiuoromethyl aryl-sulphonic acids and to a process vof preparing them; more particularly it relates to compounds corresponding with the following general formula ' 5 NHg (Cl. 260-129) the base to react in an inert organic solvent at a raised temperature. ' This reaction is the more surprising since, generally, the action of chlorosulphonic acid on tri?uoromethyl-compounds takes another course. By introducing, for instance, benzotri?uoride in to an excess of chlorosulphonic acid and allow ing the whole to stand for some time, an ex change between the tri?uoromethyl group and 10 the chlorosulphonic acid occurs in such a man SOaH wherein the benzene nucleus may be further sub stituted by halogen, alkoxy, phenoxy, benzyloxy, nitro, trifluoromethyl, alkylsulphonyl, phenyl sulphonyl or benzylsulphonyl groups. Sulphonic acids of aminotri?uoromethyl aryls have not yet been described in literature. Attempts to make these unknown sulphonic acids 20 by sulphonating aminotri?uoromethyl-aryls, for ?uoromethyl compounds the tri?uoromethyl instance, by means of concentrated sulphuric acid, sulphuric acid monohydrate or fuming sul phuric acid, at ordinary or raised temperature. group would be destroyed in a similar way. The 20 new sulphonic acids may be used as interme diates for the manufacture of dyestuffs. ' show that sulphonation does not occur. The 25 tri?uoromethyl group is saponi?ed to form the carboxylic acid group or the amine remains com The following examples illustrate the inven tion. 1. 161 grams of 1-amino-3-trifluoro-methyl pletely unchanged, and only the sulphate of the benzene are dissolved in 1000 cc. of orth'o-dichlo base is formed. The ?rst reaction occurs when sulphuric acid or sulphuric acid monohydrate is robenzene which has been carefully dried. While well stirring, 120 grams of freshly distilled chlorosulphonic acid are added by drops. The whole is then slowly heated to boiling at about 180 G. Rapid evolution of hydrochloric acid 30 used at raised temperature. By treating, for in tance, meta-aminobenzotri?uoride at 100° C. or a higher temperature with sulphuric acid of 97 per cent. strength or sulphuric acid monohy drate, then pouring on ice and working up the 35 10 ner that benzotrichloride and ?uorosulphonic acid are formed; by pouring the mixture into water, the benzotrichloride is saponi?ed with formation of benzoic acid. Thus, it is not pos sible to obtain in this manner sulphonic acid 15 derivatives of tri?uoromethyl bodies. In view of this fact, it was expected that by the action of chlorosulphonic acid on amino-substituted tri mixture, there is obtained meta-amino-benzoic acid. At a lower temperature or by using fuming sulphuric acid of 10-70 per cent, strength at any temperature and working up by pouring the mix ture on ice, there is obtained the sulphate of the By conducting the reaction with molecu lar proportions of sulphuric acid, sulphuric acid 40 base. monohydrate or fuming sulphuric acid in an or ganic solvent, for instance, in ortho-dichloro gas sets in. After about 4-5 hours the evolution of hydrochloric acid has ceased. The Whole is allowed to cool, the body which is suspended in the ortho-dichlorobenzene is ?ltered by suction, 35 washed with ether and dried. The dry powder is dissolved in 600 cc. of warm 2N-sodium carbon ate solution and 1000 cc. of water, freed from any separated unsulphonated base by extraction with ether and rendered acid to Congo‘ paper by 40 means of hydrochloric acid. The 1-amino-3-tri ?uoromethylbenzene-li-sulphonic acid produced This invention relates to a process in which chlorosulphonic acid is used as a sulphonating is thus precipitated in the form of very ?ne small white needles which are ?ltered by suction, washed with water and dried. The compound forms in the dry state a loose white powder. agent, whereby the formation of the sulphonic It corresponds with the following formula: ' benzene at l'70°—180° 0., there is obtained in most 45 cases the sulphate of the base in question. acids desired occurs in a smooth course. The re 50 action with chlorosulphonic acid may be per formed, for instance, by introducing the base to be sulphonated into an excess of chlorosulphonic acid and by carrying out the sulphonation at or dinary or raised temperature, or by causing mo 55 lecular proportions of chlorosulphonic acid and 2,119,882 2 By Working in a similar manner with l-amino 4 - trifluoromethylbenzene, 1-amino-4-tri?uoro methylbenzene-Z-sulphonic acid is obtained. 1 amino 4 2 - tri?uoromethylbenzene - 4 - sulphonic acid is obtained in a similar manner from l-am ino-2-trifluoromethylbenzene. Both acids are likewise obtained in the form of a white powder. 2. 196 grams of 1-amino-21-chlor0-5-tri?uoro methylbenzene are dropped into 1000 grams of 10 chlorosulphonic acid, while cooling with ice. A clear solution is obtained. The whole is stirred for 24 hours and the mixture is cautiously poured on ice. The separated body is ?ltered by suc tion, washed and dissolved in sodium carbonate solution and water as described in Example 1. By acidifying with hydrochloric acid, 1-amino-2 chloro- 5 -trifluoromethylbenzene- 4 -sulphonic acid is obtained in the form of ?ne small white needles. The same sulphonic acid is obtained by 20 conducting the sulphonation, as described in Ex ample 1, in chlorobenzene at 110° C. In the same manner there are obtained 1-am inc-2,4-dichloro-5-tri?uorometthylbenzenie-6-sufl phonic acid from 1-amino-2,4-dichloro-5-tri fluoro-methylbenzene, 1-amino-2,5-dichloro-3 tri?uoromethylbenzene-4-sulphonic acid from 1 amino - 2,5 - dichloro- 3 -tri?uoromethylbenzene, and 1-amino-2-bromo-5-tri?uoromethylbenzene 4-sulphonic acid from 1-amino-2-bromo-5-tri fluoromethylbenzene. 3. 196 grams of l-amino-4-chloro-2-trifluoro methylbenzene are sulphonated in 1000 cc. of chlorobenzene as described in Example 1 at 110°-120° C. After about 2 hours the evolution of hydrochloric acid gas is ?nished. After work ing up as described in Example 1, 1-amino-4 chloro - 2-trifluoromethylbenzene - G-sulphonic acid is obtained in the form of a white micro 6. 206 grams of 1-amino-2-nitro-4-tri?uoro methylbenzene are disolved in 1000 cc. of nitro benzene and 120 grams of chlorosulphonic acid are then run in. In the manner described in Example 1, the sulphonation is performed at 110° C. The sulphonic acid is ?ltered by suction, washed with ether and dried. The acid thus iso lated is a yellow powder which in the form of 10 the free acid as well as in that of the sodium salt is very easily soluble in water. By adding so dium chloride to the alkaline solution, the so dium salt of 1-amino-2-nitro~4-trifluoromethyl benzene-G-sulphonic acid is obtained in the form of yellow loose crystalline needles. By adding sodium chloride to the solution of the free sul phonic acid in water, the free sulphonic acid is obtained in the form of a loose yellow crystalline powder. . In a similar manner 1-amino-2-nitro-5-tri fluoro-methylbenzene-4-sulphonic acid is ob tained from l-amino-Z-nitro-5-tri?uoromethyl benzene and 1-amino-4-nitro~5-trifluoromethyl benzene-Z-sulphonic acid from 1-amino-4-nitr0 5-tri?uoromethylbenzene. '7. In the manner described in the foregoing examples, 230 grams of 1-amino-3,5-bis-trifluoro— methylbenzene are sulphcnated in 1000 cc. of tetrachlorethane with 120 grams of chlorosul phonic acid at 130° C. This acid, too, as well as its sodium salt, is very easily soluble in water and, when redissolved, they must be isolated by addi—' tion of a salt. 1-amino-3,5-bis-tri?uoromethyl benzene-ll-sulphonic acid is thus obtained in the 35 form of ?ne White crystals; the sodium salt forms similar crystals. In the same manner there are obtained l-am ino-2,5-bis—tri-?uoromethylbenzene-4 - sulphonic crystalline powder. acid from 1-amino-2,5-bis-tri?uoromethylben— 4. 196 grams of 1-amino-4-chloro-3-trifluoro methylbenzene are caused to react at about 160° C. with 120 grams of chlorosulphonic acid in 1000 ‘cc. of a technical mixture consisting of methylbenzene~4-sulphonic acid from 1-amino-2 ortho-dichlorobenzene and para-dichlorobenzene, in the manner described in Example 1. The sul phonation is ?nished after 2—3 hours. After working up as usual, 1-amino-4-chloro-3-tri ?uoromethylbenzene-6-sulphonic acid is obtained in the form of a white micro-crystalline powder. 5. 191 grams of ?nely powdered l-amino 2-methoxy-S-tri?uoromethylbenzene are intro duced into 1000 grams of chlorosulphonic acid. The whole is stirred, until a clear solution is ob tained and heated slowly to 120° C. After 4-5 hours the sulphonation is ?nished. The whole is poured on ice with precaution, the precipitate formed is ?ltered with suction and dissolved in warm sodium carbonate solution and water. Any (if) phonic acid from 1-amino-2..4-dimethoxy-B-tri fluoromethylbenzene. base which might be present is extracted with ether. On acidi?cation, 1-amino-2-methoxy-5 tri?uoro-methylbenzene-4-sulphonic acid is ob tained in the form of needles. zene and 1-amino-2-chloro—3,5-bis-trifluoro chloro-3,5-bis-trifluoromethylbenzene. 8. 251 grams of 1-amino-5—trifluoromethylben~ zene-2-ethylsulphone are dissolved in 1000 cc. of ortho-dichlorobenzene and 120 grams of freshly distilled chlorosulphonic acid are added by drops. The whole is then slowly heated to 120° C. and this temperture is maintained until the evolution of hydrochloric acid gas decreases. Thereupon, further 120 grams of chlorosulphonic acid are added, heating is continued at 120° C., until the I evolution of hydrochloric acid decreases, there upon a further 240 grams of chlorosulphonic acid are added. As soon as, after this last addition, 55 hydrochloric acid gas is evolved only feebly at a temperature of 120° C., the whole is allowed to cool. The separated product is ?ltered with suc tion, washed with ether and dried. It is dissolved in 600 cc. of 2N-sodium carbonate solution, the free base which might be present is removed by extraction with ether, and the double quantity by volume of saturated sodium chloride solution In a similar manner there are obtained l-am ino-4-methoxy-5—trifluoromethylbenzene-2 - sul is added to the clear aqueous solution. phonic acid from 1-arnino-4-methoxy—5—tri?uoro 2-ethylsulphone-4-sulphonic acid thus produced methylbenzene, l-arnino-~2v - ethoxy-5 - tri?uoro crystallizes in the form of white small needles which are separated from the mother liquor by ?ltering with suction and washed with saturated 70 sodium chloride solution until neutral. methylbenzene-4-sulphonic acid from l-amino 2-ethoxy-5-trifluoromethylbenzene, 1-amino-4 70 phenoxy-5-tri?uoromethylbenzene - 2 - sulphonic The so dium salt of 1-amino-5-trifluoromethylbenzene acid from 1-amino-4-phenoxy—5—tri?uorometh In a similar manner there are obtained 1 lybenzene, 1-amino-2-benzyloxy-5-trifluorometh amino-3 - tri?uoromethylbenzene - 4 - methylsul ylbenzene-ll-sulphonic acid from 1-amino-2 phone-G-sulphonic acid from 1-amino-3-tri?u benzyloxy-5-triiluoromethylbenzene, l-amino 2.4-dimethoxy-5-tri?uoromethylbenzene - 6 - sul oromethylbenzene - 4 - methylsulphone, l-amino 2-tri?uoromethylbenzene - 4 - phenylsulphone -6;. 75 2,119,882 sulphonic acid from 1-amino-2-trifluoromethyl benzene-‘l-phenylsulphone and l-amino-5-triflu oromethylbenzene-2—benzylsulphone-4- sulphonic acid from 1-amino-5-tri?uoromethylbenzene-2 benzylsulphone. Besides the indifferent organic solvents men\ tioned in the foregoing examples there may be used other solvents, for instance other halogen substitution products of the aromatic or aliphatic 3 consisting of hydrogen, halogen, alkoxy, phenoxy, benzyloxy, nitro and tri?uoromethyl and Y stands for a member of the group consisting of hydro gen, halogen and alkoxy, being crystallized com pounds which are easily soluble in aqueous alka lies and insoluble in organic solvents. 5__. The compound of the following formula: are series, such as trichlorobenzene, chlorxylenes, 1O halogenated ethanes or the like. By using any other amine of the tri?uoromethyl series the CF: sulphonation occurs in the same.manner as in the foregoing examples. 15 We claim: 1. The process of preparing aminotri?uoro methyl-benzene-sulphonic acids which comprises causing a molecular excess of chlorosulphonic acid to act upon aminotri?uoromethyl~benzenes 20 at temperatures up to about 180° C. 2. The process of preparing aminotri?uoro methyl-benzene-sulphonic acids which comprises causing chlorosulphonic acid and aminotri?uoro methyl-benzenes to react in an inert organic sol vent at temperatures of about 110° C. to about 180° C. 3. The process of preparing aminotri?uoro methyl-benzene-sulphonic acids which comprises causing molecular proportions of chlorosulphonic 30 acid and aminotri?uoromethyl—benzenes to react in an inert organic solvent at temperatures of. about 110° C. to about 180° C. 4. The compounds of the following general for mula SORH being easily soluble in aqueous alkalies and dim cultly soluble in water from which it crystallizes in the form of ?ne small white needles. 6. The compound of the following formula: NH: —Cl FaC SOaH being easily soluble in aqueous alkalies and diffi cultly soluble in water from which it crystallizes in the form of ?ne small white needles. '7. The compound of the following formula: rm Hms —No, NH: Y I CO on F: 40 86,11 wherein X stands for a member of the group 30 being a loose yellow crystalline powder which is easily soluble in water and aqueous alkalies. HERBERT KRACKER. FRITZ HERRLEIN.